Azomethine dyes



F If f j Elmore Louis Martin, Wilmi g toni' 'oirtpounds and more particularly to such com- -"dyesf An'object of this invention is to provide anew Thea'zom'ethine dyes of 'thisinvention are magenta in color and have the following for-' 15 dizing agent under alkaline conditions, e. g., ex- "niiila: I

1 1 assi iioi--- om nyfW'l w to E. I. all de fif mington, D a in 'ihvention'felate's to new organicoheini'cal This pounds whic i have tli' properties of dyes. Still i more particularly it relates to novel "azomethine "The dyestuffs of this ipvention can be prepared by reacting alower acetal, for example,

cl'assifof organic "compounds which have good 'tinctoriaipr'operties. "Aiurther object is to providea'new class 'of azomethine dyes which have "general utility in"'tl'i'e"oloring of textiles and re 10 an ethylene glycol acetal of m lp-(3-alkyl-l-pylate'd materials." Still other objectswill be ap- ""'ra'zdlyl) -benz amidolbenzaldehyde, e. g m-[p- (3-methy1-1 pyrazolyl) benza midolben'z'aldehyde, with a p-afninodialkylaniline, e. g., p-aminodiethylaniline, in the presence of a mild oxiiparent' from the following description of the in- "vention;

posed, light-sensitive silver halide, or potassium ferricyanide. 'Theacetalsused as'reactants with the p-ami- :nodialkylanilines constitute the subject matter 2010f Martin U3 S. application Ser'ia'lNo. 667,125, filed May 3, 1946',*now Patent No. 2,476,987. They are made by reacting a 5-acyloxypyrazole I containing a benzene sulfo'nyl chloride or benzene carbonyl chloride group in the 1-position of R 25' the pyrazole ring with'a lower acetal of m-aminobenzaldehyde. The reaction is preferably carried out at 'a temperature from -10 C. to

"wherein R i an alk l radical 6r 1 to 4 carbon y 30 C. in the presence of a solvent or diluent atomsyR is a hydrocarbon radical of 1 to 10 'a atoms; R areghydrogen halogen 1 medium which permits more intimate contact vymthylmethoxyli X CO of S02; and 30 between the reactants. Suitable solvents for are separately l mm gfoup of 1 4 carbbns carrying out the amidation reaction include diand together may be jdified a 5 diva oxane, acetone, methanol, ethanol, ethylene glysaturated aliphatic hydrocarbon radical of 2 to methyl ether and mlxtures of f Solvents 4 carbon atoms wherein 2 to 3 atoms only are in Wlth T reactants may be m Solutlon or the chain between the two oxygen atoms. 35 suspenslpn m the m" A i manner T In the preferred compounds of this invention, of canymg out i reactlon .conslsfis which have, the'fonowmg fairmulaz, ly addmg a solution of the acid halide 1n a water- J 1 u E misc1ble solvent to an aqugous suspension of an I aminoaldehyde or acetal'in the presence of an 4 alkali metal carbonate solution, at a temperature N-N- ..-'X-NH on i from 5 C. to 5 C.

I .l V H2 The acetals of-the lower aliphatic alcohols, i.

e., alcohols-containing 1 to 4 carbon atoms, are

02115 preferred; Included in this class are acetals of 5 aliphatic monohydric alcohols and dihydric al- 'cohols in'which the two hydroxyl groups are in 02135 1,2-' "and 1,3-positions. Of these, because of their 7 stabilitygease of obtaining in crystalline form; g; is (30 or $02, and alkyl contains 1 to icarbon I and economy, the Bthyl yw fl r P tljl wln another. class of"; preferred come-,- sorrferredil 1-:

eluted first, followed by the magenta dye.

As exemplary procedures, the m-[p-(3-alkyl- 1 pyrazolyl)benzamidolbenzaldehyde ethylene glycol acetals can be prepared by reacting the p- (3-alkyl-1-pyrazolyl) -benzoyl chloride with m aminobenzaldehyde ethylene glycol acetal. Similarly, p-(3 alkyl 1 pyrazolyDbenzenesulfonyl chloride can be reacted with m-aminobenzaldehyde ethylene glycol acetal to give the corresponding sulfonamide.

The invention is further illustrated by the following examples in which parts are by weight.

Emample I A dye is prepared from m-Ep-(S-ethylcarbonato-3-methyll-p-yrazolyly benzamido] benzaldehyde ethylene glycol acetal, described in Exampic I of application Serial No. 667,125by dispersion of 4.4 parts of the acetal and 100parts of water containing 0.8 part of sodium hydroxide and 1 part of sodium carbonate The mixture is warmed and 100 parts of 95% alcohol added. The solution is cooled to room temperature and to it is added 2 parts of p-aminodiethylaniline hydrochloride and 2 parts of sodium sulfite dissolved in 160 parts of water. A solution of 13.2 parts of potassium ferricyanide and 100 parts of water is then added dropwise with agitation. The reaction mixture is diluted with 300 parts of Water and the soluble dye collected on a filter and dried. The crudedye, weighing 5.2 parts, is recrystallized from benzene. The recrystallized dye melts at 112113 C. and has the formula:

A dye is prepared from m-[3-(3-methyl-5- benzoxypyrazolyl) 4 chlorobenzenesulfonamido] -benzaldehyde ethylene glycol aoetal prepared after the manner described in Example II of application Serial No. 667,125 by the procedure described in Example I. The crude dye obtained is purified by chromatographic separation of a methylene chloride solution of the dye in a column of lumina. The dye is completely adsorbed at the top of the column and is washed through with a methylene chloride solution containing 5% of methyl alcohol. A yellow impurity is This dye is recovered, by evaporation of the solvent, in pure form and has the formula:

In addition to the dyes included in the examples, other carbonamides and sulfonamides falling under the invention are those wherein R in Formula 1 is ethyl, propyl, butyl, hexyl, octyl, decyl, and phenyl; R and R are hydrogen, halogen, methyl, and methoxyl. They can be prepared in like manner by substitution of the appropriate reactants. Examples of these compounds are dyes prepared as described in the exhyde, m [p (3 thienyl 5 ethylcarbonatopyrazolyl) benzamido] benzaldehyde.

Other color developers which can be reacted with the pyrazolyl benzamidobenzaldehyde acetals of this invention are p-aminodimethylaniline, p-aminodipropylaniline, and p-aminodibutylaniline.

The acetals may be ethylene glycol acetals, as illustrated in the examples. They may also be acetals of methyl, ethyl, n-propyl, isopropyl, or n-butyl alcohol, or they may be acetals of 1,2- propylene glycol, 1,3-propylene glycol, and 1,3- butylene glycol. For example, they may be used to color nylon fabric by introduction of the fabric into a bath containing the dye which has been reduced with sodium hydrosulfite and stirring at -90 C. for 30 minutes to 1 hour. After removal of the cloth from the dyebath, the color is obtained by immersion in 0.5% aqueous potassium dichromate solution' In this manner brilliant magenta and purple colors are obtained that show excellent fastness to Washing. Although the vat process involving reduction is the preferred method of applying these dyes to textile fibers to achieve good penetration of color, they can also be applied directly, i. e., without prior reduction. This method is particularly applicable to the utilization of these dyes as throwster colors.

The dyes of this invention are useful as coloring materials for textiles of good wash fastness. They may be applied to cotton, viscose rayon, wool, silk or nylon fabrics by first reducing to the soluble form by methods generally employed for vat colors followed by reoxidation of the impregnated fabric with air or mild oxidizing agents.

As many widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.

What is claimed is:

l. The compounds of the formula where R is an alkyl radical of 1 to 4 carbon atoms, R is a hydrccarbon radical of .1 to 10 carbon atoms, R and R are taken from the group consisting of hydrogen, halogen taken from the group consisting of chlorine and bromine, methyl and methoxy; X is a divalent radical taken from the group consistin of CO* and ";1O; --1 g and Y are separately the same and constitute cals of 1 to 4 carboniatoms but together an alkylene radicalgof 2 to 4 carbon v h 2 to 3 carbon at'oni s i'n the chain linking th wo oxygen atoms. 2. azomethine dyes of the formula 1 1 i=0 my '4. The azomethine dyes of the formula 0-CH2 H SOr-N alkyl slkyl wherein alkyl contains 1 to 4 carbon atoms.

,5. The azomethine dye of the formula CIHI OHrJL\ /L=O Cl ELMORE. LOUIS MARTIN. I

No references cited. 

1. THE COMPOUNDS OF THE FORMULA 